Hemicyanine dyestuffs



Patented May 22, 1951 UITED STATES HEMICYANIN E DYESTUFFS Belgium No Drawing. Application March 4, 1948, Serial No. 13,081. In Great Britain March 14, 1947 8 Claims.

This invention relates to hemicyanine dyestuffs and a process of preparing same.

According to the nomenclature adopted herein, simple hemicyanine dyestuffs are such as correspond to the following general formula:

whereas dyestuffs correspondin to the following general formula:

wherein Y represents the non-metallic atoms necessary to complete a 5- or 6-membered heterocyclic ring or ring system known in the chemistry of the cyanines, R represents alkyl or aryl, X represents an acid residue, and. A represents a chemical bond or a bivalent aromatic radical, for instance, phenylene, diphenylene, napthyl ene; a bivalent radical derived from diphenyl methane, diphenyl ether, benzophenone, diphenyl amine, stilbene.

The said dyestuffs may be obtained by allowing a diamine, such as hydrazine or an aromatic diamine, to react with a quaternary salt of a heterocyclic nitrogen compound having a, reactive beta-acetyl anilido vinyl grouping, or with a Z-formyl methylene heterocyclic nitrogen-containing base.

It is the primary object of my invention to provide a new process for the preparation of a variety of hemicyanine dyestuffs.

It is another objectof my present invention to provide new unsymmetrical double hemicyanine dyestuffs.

Still another object of this invention is to provide new compounds which are symmetrical double hemicyanine dyestuffs, but substituted in the polymethine chain.

A still further object of my invention is to provide a process for the preparation of unsymmetrical double hemicyanine dyestuffs as well as symmetrical dyestuifs substituted in the polymethine chain.

A still further object. of my invention is to provide a process for the preparation of simple hemicyanine dyestuffs which are useful as intermediate products in the preparation of the double hemicyanine dyestuif above referred to.

Other objects of this invention will appear from the following description.

I have found that simple hemicyanine dye-' stuffs according to the following formula:

may be obtained by allowing an excess of a primary aromatic diamine or a salt of such a diamine to react upon intermediate products, such as cyclammonium salts, having a vinyl group or a -substituted vinyl roup linking the carbon atom in alphaor gamma-position to the N atom, with a reactive group, such as ary1-, alkylor aralkyl ether, -thioether or -se1eno ether, or an amino or substituted amino group, including acyl-, aryland acylaryl amino groupings or 2-acyl-, 2-thioacyl-, 2-formylor Z-thioformyl methylene heterocyclic N-containing bases.

Surprisingly, no symmetrical double hemicyanine dye-stuif was formed by these reactions.

I have also found that symmetrical double hemicyanines bearing substituents in the polymethine chain, or unsymmetrical double hemicyanines corresponding to the following formula:

ifying the spectral sensitivity of photographic silver halide emulsions. They are of particular wherein Y and Y represent the non-metallic atoms necessary to complete a 5- or 6-membered heterocyclic N-containing ring, which may form part of a ring system known in the chemistry of the cyanines, and may, if desired, bear one or more substituents, A represents a chemical bond or bivalent aromatic radical, R, and R represent substituted or non-substituted alkyl, alkylene or aryl, L, L1, L2, L3, L4 represent a substituted or non-substituted methine group, X and X represent an acid residue, and n and m represent 1 or 2, may be obtained by condensing said simple hemicyanine dyestuffs (Formula A) with the above defined intermediate products.

In the foregoing formula B and in the case of symmetrical dyestuffs, L1, L4 represent meth ine group, X and X represent an acid residue, and n and m represent 1 or 2, may be obtained by condensing said simple hemicyanine dyestuffs (Formula A) with the above defined intermediate products.

In the foregoing Formula B and in the case of symmetrical dyestuffs, L1, L4 represent methine groups, L2, L3 represent substituted methine groups; further, in the case of unsymmetrical dyestufis, any of the following differences may appear: Y and Y are different either by completing different rings or by completing similar rings which bear different substituents, the groups -L1=L2 and -Ls=L4 are different, R. and R are different, or X and X are different.

These double hemicyanines may also be obtained by condensing a cyclammonium salt having a reactive methylor methylene group or the corresponding methylene base simultaneously with an ortho ester and said simple hemicyanine dyestufif.

The preparation of the simple and double hemicyanines according to the invention may be illustrated by the following diagram.

4U metrical double hemicyanine dyestuffs described herein offers the advantage of including a greater number of different dyestuffs having different sensitizing properties. Hence, it is easier to find in this class a member having the sensitizing properties required for each particular purpose in view.

As already known in connection with the symmetrical hemicyanines, the hemicyanines according to the present invention may more easily be washed out of the photographic material when the diamine residue NHANH bears acid substituents, such as carboxylic or sulphonic acid groups.

These acid groups may also be introduced in 5 the R or R groups.

The following examples illustrate the present invention without limiting, however, its scope.

Example 1 11 g. 2-(beta-acetanilido-vinyl)-benzothiazolethiodide and 8 g. phenylene-diamine are dissolved in 100 cm. ethyl alcohol. This solution is refluxed for 30 minutes on the water-bath.

After cooling, the precipitate obtained is recrystallised from alcohol. Melting point is 23l-232 C. The probable formula of the simple hemicyanine is as follows:

6 To prepare an unsymmetrical double hemifrom alcohol. Melting point is 213-214 C. The cyanine dyestuff, 5 g. of this simple hemicyanine probable formula is as follows: and 5 g. 2-(beta-acetanilido-vinyl), benzoxazolethiodide are dissolved in 100 cm. ethyl alcohol. I The solution is refluxed for 30 minutes on the 5 water bath. After cooling, the unsymmetrical \N/C CH OH HN I dyestuff precipitates and is recrystallised from alcohol. Melting point is 294295, C. The proh- 0135 able formula is as follows: To prepare an unsymmetrical double hemi- S (Kg ('1-oH=oH-HNNH-o11=oH-o 2r- This dyestuff sensitizes a silver chloride emulcyanine dyestuff, 4 g. of this simple hemicyanine sion up to 540 my very strongly. and 1.5 g. 2-5-dimethyl-benzoxazol-ethiodide are heated with 0.8 g. ortho formic acid ethyl ester Example 2 for 1 hour at 130 C. on the oil bath. The reac- 8 g. 2-formy1-methylene-3-ethyl- ,3-dihydrotion mass is recrystallised from alcohol. Melting benzothiazol and 21.5 g. benzidine are dissolved point is 280-282 C. The probable formula is as in 100 cm. methyl alcohol. This solution is refollows:

fluxed for minutes on the water bath, anda This dyestufif sensitizes a silver chloride emul- HCl ga current is introduced. The intermediate sion up to 535 m very strongly. product obtained is converted with NaI to the Example 4 corresponding iodide. Melting point is 270-271 C. The probable formula is as follows: 4 Z'meta' methyl mercapto beta ethylvinyl) -benzo-thiazol-dimethyl sulphate and 3.2 g. s p-phenylene-diamine are dissolved in 85 cm. ethyl alcohol. This solution is refluxed for 30 I CCH=CH-UN-NHZ I- minutes on the boiling water bath. After adding Nf ether, the intermediate product precipitates in crystalline form. Melting point, after recrystallization from alcohol, is 220-221 C. The probable To prepare an unsymmetrical dyestuff, 2.5 g. formula is as follows. of this simple hemicyanine and 1.6 g. 2-(betaanilido-vinyl)-thiozoline-ethiodide are dissolved -s 0211' v in cm? ethyl alcohol. This solution is refluxed L J for 30 minutes on the Water bath. After cooling, y CH=" HN C TNHZ SOCHV the unsymmetrical dyestuff precipitates. Melt- N+ ing point is 235-238 C. The probable formula CH3 is as follows: 5 To prepare an unsymmetrical double hemi- T om C-CH=CHHN-C C NHCH=CHC (3H1 21-- N:

CI/ZH5 z 5 This dyestufi sensitizes a silver chloride 6111111? cyanine dye-stuff, 5 g. of this simple hemicyanine: sion up to 535 Ill u very strongly. and 5 g. '2-(beta-acetani1ido. vinyl) -henzoxazol- Example 3 60- ethiodide are dissolved in 100 cm. ethyl alcohol. This solution is refluxed for 30 minutes on the 8.7 g. 2 (beta acetanilido-vinyl)-benzoxazol- Water bath. The solution is cooled and precipiethiod de and l -p e y e amine are distated with NaI solution, and the dyestulf precipisolved in 100 om. ethyl alcohol. This solution is tated is recrystallised from alcohol. Melting refluxed for 30 minutes on the water bath. After point is 251-252 C. The probable formula is as cooling, the precipitate obtained is recrystallised follows 2.

7 8 This dyestuif very strongly sensitizes a silver the first given formula in Example 1 and 2.08 g. chloride emulsion up to 527 Inn with a maximum 2-(beta-acetanilido-vinyl) -quinoline ethyl iodide at 500 m The sensitizing maximum of a silver are dissolved in 50 cm. ethyl alcohol. This soluchloride emulsion, sensitized with 6 mg. of 3-3' tion is refluxed for 1 hour on the water bath. diethyl--5-diphenyl-9-pr0pyl oxo carbocya- 5 After cooling, the dyestufi precipitates and is nine iodide per kg. of emulsion, is raised by addrecrystallised from alcohol. Melting point is ing 30 mg. of the above mentioned unsymmetrical 230 C. (with decomposition). The probable formdyestuif per kg. ula is as follows:

s OH=CHHN NHOH=CH 2I- 1I\I+ \:N/ 02135 zHs Example 5 This dyestuf sensitizes a silver chloride emul- 5 g. 2-(beta-methyl mercapto beta-methylslon up to 545 vinyl) -benzothiazol-ethyl-methyl sulphate and. Example 8 0.5 g. p-phenylene-diamine are dissolved in 85 cm. ethyl alcohol. This solution is refluxed for 4 2-(beta-p-amino-anilido-Viny1)JOBHZOXQJ- minutes on the water bath. After cooling, the zol-ethyl iodide (intermediate product described dyestuif precipitates and is thrice recrystallised in EXa p 3), 1.5 g- 2-met y -b zyl from ethyl alcohol. Melting point is 250-252 C. 25 bromide and 0.7 g. o-formic acid ethyl ester are The probable formula is as follows: first heated at 180 C. for a while and next at 130 8 r r S t o11:oHNONH c=cH 2s 0.0m- E V 2H6 C2H5 This dyestufi alone sensitizes a silver chloride C. for 90 minutes. The product obtained is diemulsion up to 530 my weakly. In mixture with solved in alcohol, and the dyestuff is precipitated 10 mg. of 1-1-diethyl-2-2-cyanine-iodide per kg. by a KI solution 15%. After recrystallisation of emulsion, 30 mg. of the above dyestuif per kg. from alcohol, the melting point is 27'7-'-278 C. produces a high sensitizing maximum at 575 m The probable formula is as follows:

Example 6 This dyestufi sensitizes a silver bromo-chlo- 7.5 g. z-(beta-methyl mercapto beta-ethyl- 5O ride emulsion at 535 m very strongly. g g gg g xg g s iitg gif gsggg gi i g' fi It will be apparent that while I have illustrated ethyl alcohol. This solution is refluxed for 30 my invention With t e elp of Specific examples, minutes on the water bath. After cooling, the many changes may be made without departing dyestuff precipitates and is recrystallised from ethyl alcohoL Melting point is 253L259, The from the sp1r1t of the lnventlon defined 1n the probable formula is as follows: following claims.

S C2H5 (IIZHS S 1oH= ':HNC NH-o=oH-t 2s 0.013..

This dyestuff alone sensitizes a silver chloride I claim: emulsion up to 520 m very weakly. However, a 1. Process of preparing a hemicyanine dyestufi silver chloride emulsion, sensitized with 6 mg. of coresponding to the following formula: 3-3-diethyl-5-5-diphenyl-9-propyl oxo-carbocyanine iodide per kg. of emulsion, is supersensitized by adding 30 mg. of the above dyestufi Example 7 2 g. of the intermediate product according to wherein Y represents a member selected from the group consisting of the non-metallic atoms necessary to complete a and G-membered heterocyclic ring and a, 5- and G-membered heterocyclic ring system known in the chemistry of the cyanines, A represents a bivalent aromatic radical, R represents a member selected from the group consisting of alkyl and aralkyl, L1 and L2 represent a member selected from the group consisting of a methine group and a methine group substituted by alkyl, and X represents an acid residue, by reacting an excess of a primary aromatic diamine upon an intermediate product of the formula:

wherein A represents a member selected from the group consisting of hydrogen and alkyl, B represents a member selected from the group consisting of methylmercapto and acylarylamino groups, and Y, R and X have the same significance as indicated above.

2. Process of preparing the simple hemicyanine corresponding to the following formula:

gHli by reacting 2-(beta-acetanilido-vinyl) -benzothiazol-ethiodide and p-phenylene diamine upon each other, the diamine being present in excess.

3. Process of preparing the simple hemicyanine corresponding to the following formula:

by reacting Z-(beta-acetanilido-vinyl) -benzoxazol-ethiodide and p-phenylene diamine upon each other, the diamine being present in excess.

4. Process of preparing the simple hemicyanine corresponding to the following formula:

by reacting 2-(beta methyl-mercapto-betaethyl-vinyl) benzthiazol-dimethyl-sulphate and p-phenylene-diamine upon each other, the diamine being present in excess.

, Mama 1o 5. The hemicyanine dyestuff corresponding to the formula:

6. The hemicyanine dyestuff corresponding to the formula:

'7. The hemicyanine dyestufi corresponding to the formula:

H3 8. A hemicyanine dyestuff corresponding to the following formula:

,Y-\ GL1=LzNHANH X- 1% R wherein Y represents a member selected from the group consisting of the non-metallic atoms necessary to complete a 5- and 6-membered heterocyclic ring and a 5- and B-membered heterocyclic ring system known in the chemistry of the cyanines, A represents a bivalent aromatic radical, R represents a member selected from the group consisting of alkyl and aralkyl, L1 and L2 represent a member selected from the group consisting of a methine group and a methine group substituted by alkyl, and X represents an acid residue.

ANDRE EMILE VAN DORMAEL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,155,475 Duterle Apr. 25, 1931 2,155,459 Winter Apr. 25, 1939 2,307,049 Kendall Jan. 5, 1943 2,340,882 Kendall Feb. 8, 1944 2,368,305 Kendall Jan. 30, 1945 2,369,509 White Feb. 13, 1945 FOREIGN PATENTS Number Country Date 811,990 France 1937 

8. A HEMICYANINE DYESTUFF CORRESPONDING TO THE FOLLOWING FORMULA: 